JPS6021676B2 - Blue-emitting phosphors and color television cathode ray tubes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a blue light emitting crab light body and a color television cathode ray tube having a honeycomb film using this blue light emitting crab light body as a blue light emitting component crab light body.

A conventional color television cathode ray tube (hereinafter referred to as a color cathode ray tube) has a cubic silver-activated zinc sulfide backlight (cub-ZnS:A) as a blue light-emitting component backlight in the light film.
g) Or cubic silver and aluminum activated zinc sulfide crab photons (c-ZnS:Ag,N) are used as green emitting component crab photons in cubic steel and aluminum activated zinc sulfide crab photons (cube) -ZnS: Cu, AI) or copper and aluminum activated zinc sulfide cadmium phosphor [(Zn,
Cd)S:Cu,M] is a europium-activated yttrium oxysulfide phosphor (Y202S) as a red light-emitting component phosphor.
:Eu), europium-activated yttrium oxide crab photon (Y203:Eu), or europium-activated yttrium vanadate crab photon (YV04:Eu). It is desired that each color light-emitting component light body constituting the color cathode ray tube light body emit light in an appropriate component color region, have high light emission brightness, and have good stimulation current density characteristics of light emission brightness.

The above-mentioned cub-ZnS:Ag light body used as a blue light emitting component light body of a secondary color cathode ray tube and cu
b-ZnS: Among Ag, AI crab photons, c-ZnS:
The Ag crab photogen has good emission color and emission brightness, but the stimulation current density characteristics of the emission brightness are poor, while the c-rib-ZnS:A
Although the g,N type photoreceptor has good emission brightness and stimulation current density characteristics, compared to the c-rib-ZnS:Ag photoreceptor, the emitted light color is on the shorter wavelength side, and the emission brightness is also lower. In other words, the blue light emitting component of the color cathode ray tube has {1'
The x value of the CIE color system chromaticity coordinate is approximately 0.145 to 0.
．． 150 It has a luminescent color within a chromaticity region with a y value of approximately 0.055 to 0.065, ■ has high luminance, and has good stimulation current density characteristics of luminance and high stimulation current density. Although it is desired that the luminance is not saturated even when the luminance is
:Ag, the mountain crab light body is good for the above legs, but {1
It could not satisfy Hiiragi, and '2) was also inferior to the c-rib-ZnS:Ag crab photoreceptor.

Recent color cathode ray tubes have higher currents due to higher applied voltages and improvements in cathodes, getters, electron guns, etc.
The stimulation current density has become significantly higher than before.

Therefore, crab photons with good emission brightness stimulation current density characteristics have come to be preferred, and for blue light emitting component crab photons, cub, which has traditionally been used less often than ub-ZnS:Ag crab photons, has come to be preferred. -ZnS:Ag,AI pot light has attracted attention, and it has become desirable to improve the emission color and luminance of this crab light, that is, to make the emission color longer in wavelength and to improve the luminance. The present invention has been made in view of the above-mentioned circumstances, and provides a blue-emitting color cathode ray tube that has good emission color, improved emission brightness, and excellent stimulation current density characteristics of emission brightness. The object of the present invention is to provide an improved cub-ZnS:Ag, mountain crab photon that is more suitable as a component photon.

The present invention also provides the improved cube-ZnS of the present invention.
: A color cathode ray tube using Ag, AI crab photon as a blue light-emitting component crab photon and having a honeycomb film with excellent blue emission color, blue luminance and white luminance, and stimulation current density characteristics of blue luminance and white luminance. The purpose is to provide In order to achieve the above-mentioned purpose, the present inventors developed blood-ZnS:
I have conducted various studies on the mountain crab photophores.

As a result, it was discovered that a crab photon made by activating a cub-ZnS:Ag, AI crab photon with a very specific amount of steel achieves the above object, and the present invention has been completed. The blue light-emitting crab phosphor of the present invention uses ZnS as a matrix, Ag, Cu, and N as activators, and the Ag, Cu, and peak activation amounts are each 10-4 to 6 ta compared to that of the ZnS matrix. ×1
0-4 evenings, 10-7 ta to 1.5 x 10-6 evenings and 2
．． C blood-Zn with a range of 5×10-5 to 6×10-4
S: Ag, Cu, N crab light body.

Further, the color cathode ray tube of the present invention has the c-rib of the present invention.
ZnS: It is characterized by having a crab light film having a blue light emitting component as a blue light emitting component.

Conventionally, when using a c-ZnS:Ag, AI photoluminescent material as a blue light emitting component of a color cathode ray tube, Ag and the active energy level S
10-4 to 6 x 10-4 for each mother body
and 2.5 x 10-5 to 6 x 10-4 ta were used. Nevertheless, the emitted light color of this crab light body is generally included in the chromaticity region where the x value of the CIE color system chromaticity coordinates is approximately 0.145 to 0.150 and the y value is approximately 0.048 to 0.055. Therefore, the emitted light color is on the shorter wavelength side than the one desired for the blue light emitting component described above, and due to this, the emitted light brightness is also unsatisfactory. It was lower than that of the ZnS:Ag halo. This Ag and AI activation amount is ZnS matrix 1
Cubes weighing 10-4 ta to 6 x 10-4 g and 2.5 x 10-5 ta to 6 x 10-4 g for each saw, respectively.
-ZnS: Ag, AI, and Cu with an amount of 10-7 to 1.5 x 10-6 for each ZnS matrix.
Cub-ZnS of the present invention activated with: Ag, Cu, AI
The crab light body has an emission color shifted to the longer wavelength side and has an emission chromaticity point within the chromaticity region desired for the timbre light emitting component crab light body, and its luminance is also similar to that of cub-ZnS:Ag, It is significantly higher than the mountain crab phosphatica. What should be noted here is that when comparing halo bodies whose luminous colors are almost the same (that is, the x and y values are almost the same), "the crab halo of the present invention is compared to the conventional cub-ZnS: This means that the coloring luminance is several percent higher than that of Ag and crab luminance.This means that even if the luminance is only 1%, crab luminance with higher luminance is said to have higher commercial value for use in Rahfraun tubes. This is very important when considering the current state of the phosphor.If the amount of Cu activation is less than 10-7 times compared to that of the ZnS matrix, both the emission color and luminance are unfavorable; If the amount is more than 10-6 days, the luminance is good, but the emission color shifts too much to the long wavelength side, which is not preferable.
The excellent stimulation current density characteristics of luminescence brightness possessed by the S:Ag,N crab light body are maintained as they are in the crab light body of the present invention. The drawing shows that both Ag and AI activation amounts are Zn.
The amount of Cu activation and the y value of the luminescent chromaticity point for one night of ZnS matrix in the c-blood-ZnS:Ag, Cu, AI total luminous body of the present invention, which is 2 × 10-4 days for one night of S matrix connection of(
3 is a graph showing the relationship between the amount of Cu activation and the luminescence brightness (curve b) for the curve a) and the ZnS matrix 1. FIG.

Note that the luminescence brightness is determined when the Ag and AI activation amounts are both ZnS.
Conventional c blood-Z which is 2 x 10-4 per mother's blood
nS: It is shown as a relative value with the luminance of the Ag, AI crab photon as 100%. As is clear from curve a in the drawing,
The y value of the C-ZnS:Ag, Cu, wild crab photoreceptor of the present invention increases as the amount of Cu activation increases.

That is, in the blue region, a larger y value means a longer wavelength, so as the amount of Cu activation increases, the emission color gradually shifts to the longer wavelength side. And the Cu activation amount is approximately 1
It can be seen that a y value suitable for the blue light emitting component fluorophore of a color cathode ray tube can be obtained in the range of 0-7 ta to 1.5 x 10-6 t/t. Also, as is clear from curve b in the drawing,
The luminance of the c-ZnS:Ag, Cu, N backlight of the present invention gradually increases as the amount of Cu activation increases. This increase in luminance is thought to be due in part to the fact that the luminescent color gradually shifts to the longer wavelength side as the amount of Cu activation increases; however, as mentioned earlier, the luminescent luminance is Considering that it is higher than that of the c-blood-ZnS:Ag crab photoreceptor, it seems that the luminous efficiency of the crab photoreceptor was improved by activating Cu. The relationship between the Cu activation amount and the y value of the emission chromaticity point and the C
The relationship between the amount of u addition and the luminance is similar to that shown in the drawings, and based on this data, the c-rib-Z of the present invention
nS:Ag, Cu, The amount of Cu activation in the mountain halo was determined to be 10-7 to 1.5×10-6 per one day of the ZnS matrix from the viewpoint of luminescent color and luminance. c■- of the present invention
ZnS:Ag,Cu,Yamamitsu Photoform is a subsidiary cub-ZnS:Ag,AI Crabphotometer except that a carbon compound is used as a raw material for the activator Cu in addition to other raw materials. is manufactured in the same manner.

That is, first, Ag compounds such as nitrate, nitrate,
Cu compounds such as sulfates and AI compounds such as nitrates and sulfates are added and thoroughly mixed using a pole mill, mixer mill, etc. to obtain a nectar raw material mixture. It goes without saying that each activator compound is added stoichiometrically so as to provide the desired amount of each activator for the crab photoform. Further, a flux commonly used in the production of sulfide crab photons or a small amount of sulfur for oxidation prevention may be added to each of the above crab photon raw materials. Next, the obtained crab-photo material mixture is filled into a heat-resistant container such as a quartz pot or an aluminum crucible, and fired. Firing is carried out in a sulfidic atmosphere such as a hydrogen sulfide atmosphere or a sulfur atmosphere.
It is carried out at a temperature of 50 pm to 1030 qo. The firing time varies depending on the filling amount of the crab phosphor raw material mixture, the firing temperature employed, etc., but generally 30 minutes to 5 hours is appropriate. After firing, the resulting fired product is washed with water and dried to form the c-yu-yu of the present invention.
A ZnS:Ag, C-AI crab photoreceptor is obtained. In the color cathode ray tube of the present invention, the above-mentioned c-blood-ZnS:Ag, Cu, mountain crab light body of the present invention is used as the blue light emitting component crab light body of the crab light film.

As mentioned above, the c-rib-ZnS of the present invention: Ag, Cu,
Since the AI crab light body has better luminous color and luminance than the subordinate cub-ZnS:Ag,N light body, the color cathode ray tube of the present invention is superior to the blue light emitting component panel light body. - ZnS: This is due to the fact that the blue luminescent color and blue luminescent component are more intense than the conventional color cathode ray tube that has a crab luminous film using Ag, AI crab luminous material, and that the blue luminescent component is superior. Therefore, when the green and red light emitting components are the same, the white luminance is high.
In addition, the color cathode ray tube of the present invention has the same blue luminescence color as the conventional color cathode ray tube which has a crab phosphor using c rib-ZnS:Ag and crab phosphor as a blue light emitting component honey phosphor. Blue luminance is high (of course white luminance is also high). Furthermore, the color cathode ray tube of the present invention is
The stimulation current density characteristics of blue luminance are superior to conventional color cathode ray tubes using ZnS:Ag and crab photons.
For this reason, when the green and red light emitting components are the same, the stimulation current density characteristics of white light emission brightness are also excellent. The color cathode ray tube of the present invention is manufactured by the same conventional method.

Conventional cub-ZnS is used as a green light-emitting component nectar:
Ag, AI crab photon, (Zn,Cd)S:Cu,N crab photon, recently proposed cubic steel, gold and aluminum activated zinc sulfide crab photon (c■-ZnS:Cu,Ag ,A
It is preferable to use at least one of Y202S:E as the red light emitting component.
u crab photon, Y203:Eu photon and YV04:Eu
Preferably, at least one of the crab photons is used.
As explained above, the present invention provides a blue-emitting halo having excellent emission color, luminance, and stimulation current density characteristics of luminance as a blue-emitting component of a color cathode ray tube, and a blue-emitting halo which emits blue light. The present invention provides a color cathode ray tube using a component light material, and the industrial utility value of the present invention is very large.

Note that the use of the blue light-emitting crab light of the present invention is not limited to the blue light-emitting component crab light of color cathode ray tubes; for example, it can be used as the blue light-emitting component crab light of the crab light film of black-and-white television cathode ray tubes. can. Next, the present invention will be explained by examples.

Example 1 Zinc sulfide ZnS IOO silver nitrate AgN03 0.032 aluminum nitrate mountain (N03) 3.9LO
O. 28T Nitrate Steel Cu(N03)2・$LO
O. After thoroughly mixing the above raw materials using a ball mill, the mixture was filled in a quartz rubbo and fired at 970° C. for 2 hours in a hydrogen sulfide stream.

The obtained baked product was washed with water and dried. In this way A
c-rib-ZnS:Ag, Cu, mountain base light body with g, Cu, and N activation amounts of 2 × 10-4, 10-6, and 2 × 10-4, respectively, for ZnS matrix 1. I got it. This crab photon has an emission chromaticity point of (x=0.15) under electron beam excitation.
0, y = 0.065), and its luminance relative to the cyu-ZnS:Ag,N honeyluminescent body is 1.
24%, and the stimulation current density characteristics of luminescence brightness were excellent, and the luminance did not saturate even when the stimulation current density was 201 A/or higher. The luminance of this crab luminance was 103% of that of the c-ground-ZnS:Ag crab luminance, which had almost the same luminescent color. (The above emission color is CIE
It is expressed in the color system chromaticity coordinates, and the luminance is cub-ZnS:A with the same Ag and AI activation amounts.
g, cub-Z with almost the same luminous body and luminescent color
nS: It is a relative value when the light emission brightness of Ag and crab light body is set to 100%.

The same applies to the following examples. ) Next, the above c rib-ZnS:
The Ag, Cu, N halo is a blue light emitting component, and the Cu
and the AI activation amount is 1 for the ZnS matrix.
．． C-ZnS:Ag, which has a luminescence of 2 × 10-4, has a green luminescent component, and has a Eu activation amount of 5 × 10-2 compared to that of Y202S matrix 1. : A color cathode ray tube having a crab light beam in which the red light-emitting component crab light body is an Eu light body was manufactured by a conventional method.

The white brightness of this color cathode ray tube is the stimulation current density of 0.5
It was 105% under stimulation conditions of 〃A/ and acceleration voltage of 2 V. (The above white luminance is determined by using the c-rib-ZnS:Ag,AI light-emitting body with the same activation amount of Ag and AI as the blue light-emitting component crab light body, and the green and red light-emitting component crab light bodies being the same crab light body as above. This is a relative value when the white luminance of a color cathode ray tube having a rear light film using a light body is set to 100%.

The same applies to the following examples. ) Example 2 Zinc sulfide ZnS loop silver nitrate AgN03 0.0
47ta Aluminum Nitrate Mountain (N03) 3 Insect LO
O-42 nitrate steel Cu (N〇3)2・Insect L〇
0-00027 Ta Sulfur SI Example 1 Using each of the above raw materials, Ag, Cu and AI activation amounts were each 3× for ZnS matrix 1 in the same manner as in Example 1.
Cub-ZnS:Ag, Cu, AI hypophotometers with 10-4 days, 7×10-7 days and 3×10-4 days were obtained.

This crab photon has an emission chromaticity point of (x=0.1) under electron beam excitation.
48,y=0.060),
The emission brightness for the c■-ZnS:Ag,AI nectar was 125%, and the stimulation current density characteristics of the emission brightness were excellent, even when the stimulation current density was 20 peaks A/c fin or higher. The luminance was not saturated. The luminance of this saddle light body is almost the same as that of cub-ZnS:Ag.
, which was 102% of the luminance of the crab phosphor. Next, the c-blood-ZnS:Ag, Cu, N crab photoreceptor was used as a blue-emitting component photoreceptor, and the same cub-ZnS:Ag, AI crab photoreceptor and Y202S:Eu honey photoreceptor as in Example 1 were used as green and A color cathode ray tube having a crab light film with a red light emitting component crab light body was manufactured.

The white brightness of this color cathode ray tube is the stimulation current density of 0.5
The acceleration voltage 2 of the sample A/ was 106% under the stimulation condition of V. Example 3 Zinc sulfide NnS IOO Silver nitrate AgN03 0.094 Ta Aluminum nitrate M(N03)3・Insect LO
O. 84 nitrate steel Cu(N03)2・XLO
O. 00011 Sulfur SI? In the same manner as in Example 1 using each of the above raw materials, Ag, Cu and AI activation amounts were each 6× for ZnS matrix 1.
Cub-ZnS:Ag, Cu, AI crab photons with 10-4 days, 3×10-7 days and 6×10-4 days were obtained.

This crab photon has an emission color point of (x=0.1) under electron beam excitation.
48, y = 0.0 spots), and its luminescence brightness with respect to the c-rib-ZnS:Ag,AI photoreceptor was 112%, and the stimulation current density characteristics of luminescence luminance were excellent. Even when the stimulation current density exceeded 20 μA/module, the luminance did not saturate. The luminance of this crab luminescent material was 102% of the luminance of the cube-ZnS:Ag luminescent material, which had almost the same luminescent color. Next, the above c■-Z
The nS:Ag, Cu, mountain halo is used as a blue light emitting component fin light, and the same cube-ZnS:Ag, AI halo as in Example 1 and Y202S:Eu crab light are used as green and red light emitting component crab lights, respectively. A color cathode ray tube with a crab light film as a body was manufactured.

The white brightness of this color cathode ray tube is the stimulation current density of 0.5
It was 102% under stimulation conditions of 〃A/ and an acceleration voltage of 2 V.

[Brief explanation of drawings]

The drawing shows the relationship between the amount of Cu activation and the y value of the luminescent color point in the c-copy-ZnS:Ag, Cu, mountain groove light body of the present invention (curve a).
) and the relationship between Cu activation amount and luminance (curve b).

Claims (1)

[Claims] 1 Zinc sulfide is used as a base material, silver, copper and aluminum are used as activation agents, and the activation amounts of silver, copper and aluminum are each 10^-^4g to 6g per 1g of the above zinc sulfide.
×10^-^4g, 10^-^7g to 1.5×10^
-^6g and 2.5x10^-^5g to 6x10^
-^4g cubic silver, copper and aluminum activated zinc sulfide phosphor. 2 Zinc sulfide is used as a matrix, silver, copper and aluminum are used as activators, and the activation amounts of silver, copper and aluminum are respectively 10^-^4g to 6 x 10^-^4g per 1g of the above zinc sulfide. , 10^-^7g to 1.5×10
^-^6g and 2.5x10^-^5g to 6x10
A color television cathode ray tube characterized in that it has a phosphor film having a blue-emitting component phosphor having a cubic silver, copper and aluminum-activated zinc sulfide phosphor of 4g. 3. The green emitting component phosphor is a cubic copper and aluminum activated zinc sulfide phosphor, a copper and aluminum activated zinc cadmium sulfide phosphor, and a cubic copper, gold and aluminum activated zinc sulfide phosphor. the red light-emitting component phosphor is at least one of a europium-activated yttrium oxysulfide phosphor, a europium-activated yttrium oxide phosphor, and a europium-activated yttrium vanadate phosphor. A color television cathode ray tube according to claim 2, characterized in that: